EP3276046B1 - Solution de placage utilisant un sel d'ammonium - Google Patents

Solution de placage utilisant un sel d'ammonium Download PDF

Info

Publication number
EP3276046B1
EP3276046B1 EP16768889.4A EP16768889A EP3276046B1 EP 3276046 B1 EP3276046 B1 EP 3276046B1 EP 16768889 A EP16768889 A EP 16768889A EP 3276046 B1 EP3276046 B1 EP 3276046B1
Authority
EP
European Patent Office
Prior art keywords
acid
salt
ammonium salt
plating solution
plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16768889.4A
Other languages
German (de)
English (en)
Other versions
EP3276046A4 (fr
EP3276046A1 (fr
Inventor
Mami Watanabe
Kiyotaka Nakaya
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Priority claimed from PCT/JP2016/059429 external-priority patent/WO2016152986A1/fr
Publication of EP3276046A1 publication Critical patent/EP3276046A1/fr
Publication of EP3276046A4 publication Critical patent/EP3276046A4/fr
Application granted granted Critical
Publication of EP3276046B1 publication Critical patent/EP3276046B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/11—Manufacturing methods
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/4007—Surface contacts, e.g. bumps
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods
    • H01L2224/114—Manufacturing methods by blanket deposition of the material of the bump connector
    • H01L2224/1146—Plating
    • H01L2224/11462—Electroplating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H01L2224/13111—Tin [Sn] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector

Definitions

  • the present invention relates to a plating solution for tin or a tin alloy which is excellent in uniform electrodepositivity and suppresses generation of voids when a bump electrode is formed.
  • a lead-tin alloy solder plating solution made of an aqueous solution, which contains: at least one selected from an acid and a salt thereof; a soluble lead compound; a soluble tin compound; a nonionic surfactant; and a formalin condensate of naphthalenesulfonic acid or a salt thereof, is disclosed (for example, see Patent Literature 1 (PTL 1)).
  • the plating solution contains, as an additive, the formalin condensate of naphthalenesulfonic acid or the salt thereof in an amount of 0.02 to 1.50 mass% with respect to lead ions.
  • PTL 1 discloses that it is possible to form a lead-tin alloy protruding electrode, which has a small variation in the height of the surface; is smooth; and has a small variation in composition ratio of lead/tin even when plating is performed with this plating solution at a high current density.
  • a plating bath of tin or tin alloy which includes: (A) a soluble salt made of any one of a tin salt and a mixture of a tin salt and a predetermined metal salt of silver, copper, bismuth and lead; (B) an acid or a salt of the acid; and (C) a specific phenanthroline-dione compound, is disclosed (for example, see Patent Literature 2 (PTL 2)).
  • PTL 2 discloses that, by using the plating path, it is possible to have excellent uniform electrodepositivity and film appearance in the wide current density range and to obtain a uniform synthetic composition in the wide current density range.
  • a tin plating solution which includes a tin ion source; at least one kind of a nonionic surfactant; and imidazoline-dicarboxylate and 1,10-phenanthroline as additives, is disclosed (for example, see Patent Literature 3 (PTL 3)).
  • PTL 3 discloses that, by using the tin plating solution: there is no burning of plating; and excellent uniformity of the in-plane film thickness distribution is obtained, in plating of a highly-complexed printed board. Moreover, excellent uniformity of through hole plating is obtained.
  • PTL 4 describes a lead-free nickel phosphorus dispersion alloy present on a metallic substrate surface, obtainable by electroless deposition in an electrolyte containing 4 to 7 g/L of nickel ions; 15 to 40 g/L of hypophosphite; at least one stabilizer; 5 to 400 mg/L of an alkylaryl oxydialkyl benzyl ammonium chloride or a partially fluorinated betaine; 50 to 60 g/L of a carboxylic acid-containing complexing agent A; 5 to 40 g/L of a carboxylic acid-containing complexing agent B different from A; 4 to 10 g/L of dispersed particles which differ from the composition of the nickel/phosphorus alloy; and no boric acid or borates the data relating to the composition of the electrolyte as a whole.
  • PTL 5 describes an aqueous electroplating bath solution for filling large high aspect ratio recessed features with copper, without depositing a thick layer of copper in the field region, the aqueous solution comprising: (a) copper ions; and (b) an organic dual state inhibitor configured for inhibiting deposition of copper in the field region, wherein the organic dual state inhibitor is a quarternary ammonium salt, having one or more alkyl or aralkyl N-substituents with at least seven carbon atoms.
  • the uniform electrodeposition property of the tin or tin alloy plating solution has been improved by the additives described in the above-mentioned PTLs 1 to 3.
  • the demand for an improved quality of the plating film is increased; and further improvement of uniform electrodepositivity is needed.
  • the bump electrodes which are provided on a board for connecting a semiconductor device in the flip-chip mounting, are formed by the plating method, empty space called voids are occasionally formed in the inside of the bumps after the reflow treatment. Since formation of these voids could cause occurrence of contact failure, formation of bumps free of the void is needed.
  • improving the uniform electrodepositivity and suppressing the occurrence of voids are in conflicting relationships.
  • the uniform electrodepositivity can be improved by increasing the polarization resistance of the electrode surface, while the occurrence of voids is suppressed by reducing the overvoltage of the cathode.
  • an additive for a plating solution satisfying both characteristics has been demanded.
  • the purpose of the present invention is to provide a plating solution for tin or tin alloy which is excellent in uniform electrodepositivity and suppresses occurrence of voids when a bump electrode is formed.
  • the first aspect of the present invention is a plating solution including: (A) a soluble salt containing at least a stannous salt; (B) an acid selected from organic acid and inorganic acid or a salt of the acid; and (C) an additive, wherein the additive includes an ammonium salt selected from the following ammonium salts: an ammonium salt represented by a general formula (3) , an ammonium salt represented by a general formula (4), and an ammonium salt represented by a general formula (5) below
  • the second aspect of the present invention is the plating solution according the first aspect of the present invention, wherein the additive further includes a nonionic surfactant represented by a general formula (2) below.
  • a nonionic surfactant represented by a general formula (2) below.
  • R 3 and R 4 is the group represented by the formula (A) below; Y 1 and Y 2 represent a single bond or a group selected from ⁇ O-, -COO- and ⁇ CONH-; and Z represents a benzene ring or 2,2-diphenylpropane, and in the formula (A), n indicates 2 or 3 and m indicates an integer from 1 to 15. ⁇ (C n H 2n ⁇ O) m ⁇ H (A)
  • the third aspect of the present invention is the plating solution according to the first or second aspect of the present invention, further including an additional additive of a complexing agent, a brightener, or an antioxidant.
  • the uniform electrodepositivity can be improved in the wide current density range; occurrence of the void in formation of the bump electrode can be suppressed; and a plating film, which has a good appearance and is highly reliable, can be formed.
  • products which are applicable to a narrow pitch and a complicated wiring pattern at a high quality, can be produced.
  • the nonionic surfactant represented by the above-indicated formula (2) by further including the nonionic surfactant represented by the above-indicated formula (2), occurrence of the void in formation of the bump electrode can be suppressed; and the variation in the thickness of the plating film can be reduced further.
  • the technical effect explained below can be obtained.
  • the brightener imparts gross to the plating film.
  • the complexing agent stabilizes the noble metal ions in the bath by the plating solution including noble metal such as silver and the like; and homogenizes the composition of the precipitated alloy.
  • the antioxidant prevents oxidation of the soluble stannous salt to tin dioxide salt.
  • the plating solution of the first aspect of the present invention is a plating solution for tin or tin alloy, and includes: (A) a soluble salt containing at least a stannous salt; (B) an acid selected from organic acid and inorganic acid or a salt of the acid; and (C) an additive.
  • the additive includes a specific ammonium salt selected from an ammonium salt represented by a general formula (3), an ammonium salt represented by a general formula (4), and an ammonium salt represented by a general formula (5) below.
  • the soluble salt is made of any one of: the stannous salt; and the mixture of the stannous salt and a metal salt selected from the group consisting of silver, copper, bismuth, nickel, antimony, indium, and zinc.
  • R 1 indicates C n H 2n+1 , n being an integer of 8 to 16, R 2 and R 3 are identical or different, and indicate C n H 2n+1 , n being an integer of 1 to 2, X represents a halogen, and Y represents (CH 2 -CH 2 -O) n , n being an integer of 1 to 2.
  • the tin alloy included in the plating solution of the present invention is an alloy of: tin; and a predetermined metal selected from silver, copper, bismuth, nickel, antimony, indium and zinc.
  • a predetermined metal selected from silver, copper, bismuth, nickel, antimony, indium and zinc.
  • Examples thereof include: binary alloys such as the tin-silver alloy, the tin-copper alloy, the tin-bismuth alloy, the tin-nickel alloy, the tin-antimony alloy, the tin-indium alloy, and the tin-zinc alloy; and ternary alloy such as the tin-copper-bismuth, the tin-copper-silver alloy and the like.
  • the soluble salt (A) included in the plating solution of the present invention can be any soluble salt that forms varieties of metal ions such as Sn 2+ , Ag + , Cu + , Cu 2+ , Bi 3+ , Ni 2+ , Sb 3+ , In 3+ , Zn 2+ in the plating solution.
  • it includes: an oxide and a halide of the metal; and a salt formed between an inorganic acid or an organic acid and one of the above-described metals.
  • Examples of the metal oxide include stannous oxide, copper oxide, nickel oxide, bismuth oxide, antimony oxide, indium oxide, zinc oxide and the like
  • examples of the metal halide include stannous chloride, bismuth chloride, bromide Bismuth, cuprous chloride, cupric chloride, nickel chloride, antimony chloride, indium chloride, zinc chloride and the like.
  • Examples of the metal salt with the inorganic acid or an organic acid include copper sulfate, stannous sulfate, bismuth sulfate, nickel sulfate, antimony sulfate, bismuth nitrate, silver nitrate, copper nitrate, antimony nitrate, indium nitrate, nickel nitrate, zinc nitrate, copper acetate, nickel acetate, nickel carbonate, sodium stannate, stannous fluoroborate, stannous methanesulfonate, silver methanesulfonate, copper methanesulfonate, bismuth methanesulfonate, nickel methanesulfonate, indium metasulfonate, bismethane zinc sulfonate, stannous ethanesulfonate, bismuth 2-hydroxypropanesulfonate, and the like.
  • the acid or the salt thereof (B) included in the plating solution of the present invention is selected from organic acid and inorganic acid, or the salt of one of these acids.
  • organic acid include: organic sulfonic acids such as alkanesulfonic acid, alkanol sulfonic acid and aromatic sulfonic acid; and aliphatic carboxylic acids.
  • inorganic acids include: borofluoric acid, hydrosilicofluoric acid, sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and the like.
  • the salt includes: a salt of an alkali metal, a salt of an alkaline earth metal, an ammonium salt, an amine salt, a sulfonate and the like.
  • the component (B) is preferably an organic sulfonic acid from the viewpoint of the solubility of the metal salt and ease of wastewater treatment.
  • examples thereof include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid and the like, as well as hexanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid and the like.
  • examples thereof include 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 2-hydroxybutane- 1 -sulfonic acid, 2-hydroxypentane- 1 -sulfonic acid, as well as 1-hydroxypropane-2-sulfonic acid, 3-hydroxypropane-1-sulfonic acid, 4-hydroxybutane-1-sulfonic acid, 2-hydroxyhexane-1-sulfonic acid, 2-hydroxydecane-1-sulfonic acid, 2-hydroxydodecane-1-sulfonic acid and the like.
  • the above-mentioned aromatic sulfonic acid is benzenesulfonic acid, alkylbenzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid and the like.
  • examples thereof include 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, toluenesulfonic acid, xylene sulfonic acid, p-phenolsulfonic acid, cresolsulfonic acid, sulfosalicylic acid, nitrobenzene sulfonic acid, sulfobenzoic acid, diphenylamine-4-sulfonic acid and the like.
  • aliphatic carboxylic acid examples include acetic acid, propionic acid, butyric acid, citric acid, tartaric acid, gluconic acid, sulfosuccinic acid, trifluoroacetic acid and the like.
  • ammonium salts 3, 4 and 5 are ammonium salts used in the present invention and one of them is included in the plating solution of the present invention.
  • the ammonium salt 1 is N,N-dimethyl-N-[2-[2-[[4-(1,1,3,3-tetramethylbutyl) phenyl] oxy] ethoxy] ethyl] benzenemethanaminium.
  • X is chlorine Y represents (CH 2 -CH 2 -O) 2 .
  • the ammonium salt 1 is represented by the formula below.
  • the ammonium salt 2 is N,N-dimethyl-N-[2-[2-[[4-(tetradecyl) phenyl] oxy] benzenemethanaminium.
  • X is chlorine and Y represents CH 2 -CH 2 -O.
  • the ammonium salt 2 is represented by the formula below.
  • the ammonium salt 3 is N,N-dimethyl-N-[2-[2-[[4-(1,1,3,3-tetramethyloctyl) phenyl] oxy] ethoxy] ethyl] benzenemethanaminium.
  • R 2 and R 3 are CH 3
  • X is chlorine
  • Y represents (CH 2 -CH 2 -O) 2 .
  • the ammonium salt 3 is represented by the formula below.
  • the ammonium salt 4 is N,N-dimethyl-N-[2-[2-[[4-(1,1,3,3-tetramethylhexyl) phenyl] oxy] ethoxy] ethyl] benzenemethanaminium.
  • R 2 and R 3 are CH 3
  • X is bromine
  • Y represents (CH 2 -CH 2 -O) 2 .
  • the ammonium salt 4 is represented by the formula below.
  • the ammonium salt 5 is N,N-diethyl-N-[2-[2-[[4-(tetrahexyl) phenyl] oxy] benzenemethanaminium.
  • R 2 and R 3 are C 2 H 5
  • X is chlorine
  • Y represents (CH 2 -CH 2 -O) 2 .
  • the ammonium salt 5 is represented by the formula below.
  • the ammonium salt 6 is N,N-dimethyl-N-[2- [2-[[4-tetrabutylphenyl] oxy] ethoxy] ethyl] benzenemethanaminium.
  • R 2 and R 3 are CH 3
  • X is chlorine
  • Y represents (CH 2 -CH 2 -O) 2 .
  • the ammonium salt 6 is represented by the formula below.
  • the ammonium salt 7 is N,N-dimethyl-N-[2-[2-[[4-(1,1,3,3-tetramethyloctyl) phenyl] oxy] ethoxy] ethyl] benzenemethanaminium.
  • R 2 and R 3 are CH 3
  • X is chlorine
  • Y represents (CH 2 -CH 2 -O) 2 .
  • the ammonium salt 7 is represented by the formula below.
  • the plating solution of the present invention preferably further includes a nonionic surfactant represented by the following formula (2) as another additive.
  • a nonionic surfactant represented by the following formula (2) as another additive.
  • R 3 and R 4 are groups represented by the following formula (A).
  • Y 1 and Y 2 are groups selected from: a single bond; and a group selected from ⁇ O-, -COO- and -CONH-.
  • Z represents a benzene ring or 2,2-diphenylpropane.
  • n is 2 or 3.
  • m is an integer of 1 to 15. ⁇ (C n H 2n ⁇ O) m ⁇ H (A)
  • the nonionic surfactant represented by formula (2) included in the plating solution of the present invention are as follows.
  • the nonionic surfactant 1 represented by the formula (2) is polyoxyethylene bisphenol ether.
  • the substituent R 3 is H-(CH 2 -CH 2 -O) p (p is an integer of 2 to 10)
  • Y 1 is -O-
  • Z is (C 6 H 10 )C 3 H 4 (C 6 H 10 )
  • Y 2 is -O-.
  • R 4 is H-(CH 2 -CH 2 -O) p (p is an integer from 2 to 10) and is represented by the following formula.
  • the nonionic surfactant 2 represented by the formula (2) is polyoxyethylene phenyl ether.
  • the substituent R 3 is H-(CH 2 -CH 2 -O) q (q is an integer of 2 to 15).
  • Y 1 is -O-.
  • Z is C 6 H 10
  • Y 2 is a single bond
  • R 4 is CH 2 -CH 2 -OH, and is represented by the following formula.
  • the plating solution of the present invention preferably further includes, as other additives, a surfactant, a complexing agent and/or an antioxidant other than the above.
  • surfactants in this case include ordinary anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.
  • anionic surfactant examples include: polyoxyalkylene alkyl ether sulfates such as polyoxyethylene (containing 12 mol of ethylene oxide) nonyl ether sodium sulfate; polyoxyethylene alkyl ether sulfate such as polyoxyethylene (containing 12 mol of ethylene oxide) dodecylphenyl ether sodium sulfate; alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate, naphthol sulfonates such as sodium 1-naphthol-4-sulfonate and disodium 2-naphthol-3,6-disulfonate; naphthol sulfonate salts such as sodium 1-naphthol-4-sulfonate and disodium 2-naphthol-3,6-disulfonate; (poly) alkylnaphthalenesulfonic acid salts such as sodium diisopropy
  • cationic surfactant examples include mono to tri alkylamine salts, dimethyldialkylammonium salt, trimethylalkylammonium salt, dodecyltrimethylammonium salt, hexadecyltrimethylammonium salt, octadecyltrimethylammonium salt, dodecyldimethylammonium salt, octadecenyl Dimethyl ethyl ammonium salt, dodecyl dimethyl benzyl ammonium salt, hexadecyl dimethyl benzyl ammonium salt, octadecyl dimethyl benzyl ammonium salt, trimethyl benzyl ammonium salt, triethyl benzyl ammonium salt, hexadecyl pyridinium salt, dodecyl pyridinium salt, dodecyl picolinium salt, dodecylimidazolinium salt, oleyl imidazolinium
  • nonionic surfactant examples include, a sugar ester, fatty acid ester, C1 to C25 alkoxyl phosphate (salt), sorbitan ester, C1 to C22 aliphatic amide and the like, to which 2 to 300 moles of ethylene oxide (EO) and/or propylene oxide (PO) are additionally condensed.
  • examples of the nonionic surfactant include the sulfuric acid adduct or the sulfonate adduct of a condensation product of: silicon-based polyoxyethylene ether, silicon-based polyoxyethylene ester, fluorine-based polyoxyethylene ether, fluorine-based polyoxyethylene ester, ethylene oxide and/or propylene oxide; and alkylamine or diamine.
  • amphoteric surfactant examples include betaine, carboxybetaine, imidazolinium betaine, sulfobetaine, aminocarboxylic acid and the like.
  • the above-described complexing agent is used for stabilizing noble metal ions and the like in the bath with the plating solution including a noble metal such as silver and homogenizing the composition of the precipitated alloy.
  • the complexing agent include oxycarboxylic acid, polycarboxylic acid, monocarboxylic acid and the like.
  • gluconic acid citric acid, glucoheptonic acid, gluconolactone, glucoheptolactone, formic acid, acetic acid, propionic acid, butyric acid, ascorbic acid, oxalic acid, malonic acid, succinic acid, glycolic acid, malic acid, Tartaric acid, diglycolic acid, thioglycolic acid, thiodiglycolic acid, thioglycol, thiodiglycol, mercaptosuccinic acid, 3,6-dithia-1,8-octanediol, 3,6,9-trithiadecane-1,11-disulfonic acid, thiobis (dodecaethylene glycol), di(6-methylbenzothiazolyl) disulfide trisulfonic acid, di(6 - chlorobenzothiazolyl) disulfide disulfonic acid, gluconic acid, citric acid, glucohepton
  • conductive salt examples include sodium salt, potassium salt, magnesium salt, ammonium salt, amine salt and the like of sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, sulfonic acid.
  • the brightener is used to impart gloss to the plating film.
  • the brightener include: varieties of aldehydes such as benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxy-aldehyde, 3-acenaphthoaldehyde, benzylideneacetone, pyridideneacetone, furfurylideneacetone, cinnamaldehyde, anisaldehyde, salicylaldehyde, crotonaldehyde, acrolein, glutaraldehyde, paraldehyde, vanillin; benzothiazoles such as triazine, imidazole, in
  • the antioxidant is used to prevent oxidation of soluble stannous salt to tin dioxide salt.
  • examples of the antioxidant include hypophosphorous acids, ascorbic acid or the salts thereof, phenol sulfonic acid (Na), cresolsulfonic acid (Na), hydroquinone sulfonic acid (Na), hydroquinone, ⁇ or ⁇ -naphthol, catechol, resorcinol, phloroglucin, hydrazine, phenolsulfonic acid, catecholsulfonic acid, hydroxybenzenesulfonic acid, naphtholsulfonic acid, the salts thereof, and the like.
  • the ammonium salt (C) included in the plating solution of the present invention can be used singly or in combination, and the content in the plating solution is 0.1 to 10 g/L, preferably 1 to 2 g/L. If the content is less than the appropriate range, uniform electrodepositivity and effect of improving the film appearance cannot be obtained sufficiently, whereas if it is too much, burning of plating may occur.
  • the predetermined soluble metal salt (A) can be used singly or in combination, and the content thereof in the plating solution is 30 to 100 g/L, preferably 40 to 60 g/L. When the content is less than the appropriate range, productivity drops. As the content increases, the cost of the plating solution increases.
  • the inorganic acid, the organic acid or the salt thereof (B) can be used singly or in combination, and the content thereof in the plating solution is 80 to 300 g/L, preferably 100 to 200 g/L. If the content is less than the appropriate range, the conductivity decreases; and the voltage increases. When the content increases, the viscosity of the plating solution rises and the agitation speed of the plating solution decreases.
  • the additive concentrations of the above-described components (A) to (C) are arbitrarily adjusted/selected according to the plating method such as barrel plating, rack plating, high-speed continuous plating, rackless plating, bump plating and the like.
  • the liquid temperature of the electroplating solution of the present invention is generally 70°C or less, preferably 10 to 40°C.
  • the cathode current density is generally 0.01 to 150 A/dm 2 , preferably 0.1 to 100 A/dm 2 .
  • a predetermined metal film can be formed on an electronic component by applying the plating solution of tin or tin alloy containing the ammonium salt included in the plating solution of the present invention to the electronic component to be plated.
  • the electronic parts include a printed circuit board, a flexible printed circuit board, a film carrier, a semiconductor integrated circuit, a resistor, a capacitor, a filter, an inductor, a thermistor, a quartz oscillator, a switch, a lead wire, and the like.
  • Reference Example 1 is an example of a tin plating solution containing the ammonium salt 1;
  • Reference Example 2 is an example of a tin-silver alloy plating solution containing the ammonium salt 2;
  • Example 3 is an example of a tin-silver alloy plating solution containing an ammonium salt 3;
  • Example 4 is an example of a tin plating solution containing the ammonium salt 4;
  • Example 5 is an example of a tin-copper alloy plating solution containing the ammonium salt 5; and
  • Example 6 is a tin-zinc alloy plating solution containing the ammonium salt 5.
  • Reference Example 1, Example 4 of the present invention and Comparative Example 1 are acidic tin plating solutions
  • Comparative Example 2 is an acidic tin alloy plating solution.
  • a commercially available Hull cell tester manufactured by Yamamoto Plating Test Instrument Co., Ltd.
  • a copper hulled cell plate (length 70 mm, width 100 mm, thickness 0.3 mm) was used as a substrate to be plated.
  • the plating solution was placed in a Hull cell tester, the liquid temperature was set to 25°C, and the energizing current was 2A.
  • the plating time was 5 minutes and the plating solution was not stirred during the plating process.
  • the hull cell evaluation was made according to the presence or absence of burning of plating on the plated hull cell plate.
  • a copper substrate (10 cm in length, 10 cm in width, 0.3 mm in thickness) was immersed in a plating solution at a liquid temperature of 25°C and subjected to a current density of 5 A/ dm 2 for 1 minute.
  • the film thickness of 10 places of the obtained plating film was measured with a fluorescent X-ray film thickness measuring device (manufactured by SII NanoTechnology Inc.).
  • the standard deviation (3 ⁇ ) of the film thickness at ten places was calculated, and it was evaluated whether the plating film thickness variation, that is, the electrodeposition was performed uniformly.
  • a copper substrate (10 cm in length, 7 cm in width, 0.3 mm in thickness) was immersed in a plating solution at a liquid temperature of 25°C and energized at a current density of 3 A/dm 2 for 13 minutes to form a plating film on the substrate.
  • the center of the substrate with the plating film was cut into square pieces of 10 mm in length and 10 mm in width. Simulating the reflaw treatment, these pieces were heated in a nitrogen atmosphere with a hot plate until the surface temperature of the substrate reached 270°C, and then rapidly cooled after retaining them at the raised temperature for 20 seconds.
  • Evaluation of voids was conducted by: observing the plating film after reflow with transmission X-ray; and calculating the void area ratio by dividing the area occupied by the void by the area of the small pieces of 10 mm in length and 10 mm in width. The presence or absence of the voids was evaluated based on the above-described void area ratio, and when the void area ratio was 0.1% or more, it was defined as voids being generated.
  • the plating solution of the present invention can be applied to electronic components such as printed boards, flexible printed boards, film carriers, semiconductor integrated circuits, resistors, capacitors, filters, inductors, thermistors, crystal resonators, switches, lead wires and the like; and a part of electronic component such as the bump electrode of the wafer.
  • electronic components such as printed boards, flexible printed boards, film carriers, semiconductor integrated circuits, resistors, capacitors, filters, inductors, thermistors, crystal resonators, switches, lead wires and the like; and a part of electronic component such as the bump electrode of the wafer.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Claims (3)

  1. Solution de placage comprenant :
    (A) un sel soluble contenant au moins un sel stanneux ;
    (B) un acide choisi parmi un acide organique et un acide inorganique ou un sel de celui-ci ; et
    (C) un additif, dans laquelle
    l'additif comprend un sel d'ammonium choisi parmi les sels d'ammonium suivants : un sel d'ammonium représenté par une formule générale (3), un sel d'ammonium représenté par une formule générale (4), et un sel d'ammonium représenté par une formule générale (5) ci-dessous,
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
  2. Solution de placage selon la revendication 1, dans laquelle
    l'additif comprend en outre un tensioactif non ionique représenté par une formule générale (2) ci-dessous,

            R3―Y1―Z―Y2―R4     (2)

    et dans laquelle, dans la formule (2), R3 et R4 sont le groupe représenté par la formule (A) ci-dessous,

            ―(CnH2n―O)m―H     (A)

    et dans laquelle Y1 et Y2 représentent une liaison simple ou un groupe choisi parmi -O-,
    -COO- et -CONH- ; et Z représente un cycle benzénique ou du 2,2-diphénylpropane, et dans la formule (A), n indique 2 ou 3 et m indique un nombre entier de 1 à 15.
  3. Solution de placage selon la revendication 1 ou 2, comprenant en outre un additif supplémentaire parmi un agent complexant, un brillanteur ou un antioxydant.
EP16768889.4A 2015-03-26 2016-03-24 Solution de placage utilisant un sel d'ammonium Active EP3276046B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2015064073 2015-03-26
JP2016056776A JP6631349B2 (ja) 2015-03-26 2016-03-22 アンモニウム塩を用いためっき液
PCT/JP2016/059429 WO2016152986A1 (fr) 2015-03-26 2016-03-24 Solution de placage utilisant un sel d'ammonium

Publications (3)

Publication Number Publication Date
EP3276046A1 EP3276046A1 (fr) 2018-01-31
EP3276046A4 EP3276046A4 (fr) 2018-11-21
EP3276046B1 true EP3276046B1 (fr) 2021-12-01

Family

ID=57242647

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16768889.4A Active EP3276046B1 (fr) 2015-03-26 2016-03-24 Solution de placage utilisant un sel d'ammonium

Country Status (6)

Country Link
US (1) US10450665B2 (fr)
EP (1) EP3276046B1 (fr)
JP (1) JP6631349B2 (fr)
KR (1) KR20170131418A (fr)
CN (1) CN107406999B (fr)
TW (1) TWI694178B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107708315B (zh) * 2017-10-31 2020-01-17 江苏贺鸿电子有限公司 一种镶嵌陶瓷的散热线路板及其制备方法
ES2823149T3 (es) * 2017-12-22 2021-05-06 Atotech Deutschland Gmbh Un método para incrementar la resistencia a la corrosión de un sustrato que comprende una capa externa de aleación de cromo
JP2024500292A (ja) * 2020-11-20 2024-01-09 コリア インスティテュート オブ インダストリアル テクノロジー 錫－銀めっき液及びそれを用いた錫－銀はんだバンプの形成方法
CN115161725A (zh) * 2022-06-23 2022-10-11 南通赛可特电子有限公司 一种半光亮电酸性镀锡添加剂、制备方法及应用

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102755A (en) 1973-06-01 1978-07-25 Langbein-Pfanhauser Werke Ag Method of and electrolytic bath for the electrodeposition of semibright nickel and nickel-cobalt coatings upon a metal surface
JPH02197580A (ja) * 1989-01-24 1990-08-06 Okuno Seiyaku Kogyo Kk 無電解ハンダめっき浴
JP3871013B2 (ja) 1998-11-05 2007-01-24 上村工業株式会社 錫−銅合金電気めっき浴及びそれを使用するめっき方法
US6508927B2 (en) 1998-11-05 2003-01-21 C. Uyemura & Co., Ltd. Tin-copper alloy electroplating bath
JP4186030B2 (ja) 1999-03-16 2008-11-26 石原薬品株式会社 無電解スズ−銀合金メッキ浴及び当該メッキ浴でスズ−銀合金皮膜を施したｔａｂのフィルムキャリア等
JP3455712B2 (ja) * 2000-04-14 2003-10-14 日本ニュークローム株式会社 銅−スズ合金めっき用ピロリン酸浴
JP4880138B2 (ja) * 2001-07-13 2012-02-22 石原薬品株式会社 スズメッキ浴、スズメッキ方法及び当該メッキ浴を用いてスズメッキを施した電子部品
JP4441726B2 (ja) 2003-01-24 2010-03-31 石原薬品株式会社 スズ又はスズ合金の脂肪族スルホン酸メッキ浴の製造方法
JP4582294B2 (ja) 2004-04-02 2010-11-17 三菱マテリアル株式会社 鉛−スズ合金ハンダめっき液
DE102004047423C5 (de) * 2004-09-28 2011-04-21 AHC-Oberflächentechnik GmbH & Co. OHG Außenstromlos aufgebrachte Nickellegierung und ihre Verwendung
US7713859B2 (en) 2005-08-15 2010-05-11 Enthone Inc. Tin-silver solder bumping in electronics manufacture
ES2361500T3 (es) * 2006-01-06 2011-06-17 Enthone, Incorporated Electrolíto y procedimiento para la precipitación de una capa metálica mate.
PL1948769T3 (pl) * 2006-07-31 2009-08-31 Reckitt Benckiser Uk Ltd Ulepszone kompozycje do czyszczenia twardych powierzchni
EP2175048A1 (fr) 2008-10-13 2010-04-14 Atotech Deutschland Gmbh Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat
TWI523976B (zh) * 2010-05-19 2016-03-01 諾菲勒斯系統公司 利用具有雙態抑制劑的電解液之矽穿孔填充
JP5574912B2 (ja) 2010-10-22 2014-08-20 ローム・アンド・ハース電子材料株式会社 スズめっき液
JP5412612B2 (ja) 2011-08-22 2014-02-12 石原ケミカル株式会社 スズ及びスズ合金メッキ浴、当該浴により電着皮膜を形成した電子部品
US9604316B2 (en) * 2014-09-23 2017-03-28 Globalfoundries Inc. Tin-based solder composition with low void characteristic

Also Published As

Publication number Publication date
US10450665B2 (en) 2019-10-22
EP3276046A4 (fr) 2018-11-21
JP6631349B2 (ja) 2020-01-15
JP2016183411A (ja) 2016-10-20
TWI694178B (zh) 2020-05-21
TW201700797A (zh) 2017-01-01
CN107406999B (zh) 2019-08-27
CN107406999A (zh) 2017-11-28
KR20170131418A (ko) 2017-11-29
EP3276046A1 (fr) 2018-01-31
US20180057953A1 (en) 2018-03-01

Similar Documents

Publication Publication Date Title
EP0503389B1 (fr) Procédé de dépÔt chimique d'étain de plomb ou d'alliage étain plomb
EP1754805B1 (fr) Solution électrolytique de zinc et méthode d'électroplacage de zinc
EP3276046B1 (fr) Solution de placage utilisant un sel d'ammonium
US6176996B1 (en) Tin alloy plating compositions
US20080173550A1 (en) Method for forming a displacement tin alloy plated film, displacement tin alloy plating bath and method for maintaining a plating performance
JP5150016B2 (ja) スズ又はスズ合金メッキ浴、及び当該メッキ浴を用いたバレルメッキ方法
JP2013044001A (ja) スズ及びスズ合金メッキ浴、当該浴により電着皮膜を形成した電子部品
EP3276045B1 (fr) Solution de placage avec du sel de phosphonium
JP2017179515A (ja) めっき液
EP3604622A1 (fr) Liquide de placage
EP3276047B1 (fr) Solution de placage utilisant du sel de sulfonium
JP2018123402A (ja) アンモニウム塩を用いためっき液
WO2016152983A1 (fr) Solution de placage avec du sel de phosphonium
WO2016152986A1 (fr) Solution de placage utilisant un sel d'ammonium
WO2016152997A1 (fr) Solution de placage utilisant du sel de sulfonium
JPH1036973A (ja) 無電解スズメッキ浴、及び当該メッキ浴を用いてスズメッキ皮膜を形成したｔａｂのフィルムキャリア
CN116157555A (zh) 氰系电解银合金镀液

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170925

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20181019

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 3/60 20060101ALN20181015BHEP

Ipc: H01L 21/60 20060101AFI20181015BHEP

Ipc: H05K 3/18 20060101ALI20181015BHEP

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MITSUBISHI MATERIALS CORPORATION

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: H01L 21/60 20060101AFI20210419BHEP

Ipc: H05K 3/18 20060101ALI20210419BHEP

Ipc: C25D 3/32 20060101ALI20210419BHEP

Ipc: C25D 3/60 20060101ALN20210419BHEP

INTG Intention to grant announced

Effective date: 20210518

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602016066835

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C25D0003320000

Ipc: H01L0021600000

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: H01L 21/60 20060101AFI20210708BHEP

Ipc: H05K 3/18 20060101ALI20210708BHEP

Ipc: C25D 3/32 20060101ALI20210708BHEP

Ipc: C25D 3/60 20060101ALN20210708BHEP

INTG Intention to grant announced

Effective date: 20210803

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1452609

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211215

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016066835

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20211201

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1452609

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220301

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220314

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220301

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220302

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220401

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016066835

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220401

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20220902

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220324

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220324

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220324

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602016066835

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211201